Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST )

Hrovat, David A.; Wang, Xue-Bin; Borden, Weston Thatcher

doi:10.1002/poc.3824

Title: Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH ₂ is predicted to increase the singlet-triplet energy difference ( ΔE _ST )

Journal Article · Tue Feb 20 00:00:00 EST 2018 · Journal of Physical Organic Chemistry

DOI:https://doi.org/10.1002/poc.3824· OSTI ID:1508275

^[1];

^[2];

^[1]

Department of Chemistry and the Center for Advanced, Scientific Computing and Modeling, University of North Texas, Denton TX USA
Physical Sciences Division, Pacific Northwest National Laboratory, Richland WA USA

CASSCF and CASPT2 calculations have been performed on the triplet and two lowest-lying singlet states of the 2,7-naphthoquinodimethane (NQDM) and 2,7-naphthoquinone (NQ) diradicals. Both diradicals are predicted to have triplet ground states but to differ in the ordering of the two lowest singlet states, with E(1A1) < E(1B2) in NQDM, but E(1A1) > E(1B2) in NQ. The reason for the difference in ordering of the singlet states in these two diradicals is discussed. The state reordering is shown to be responsible for the prediction that the substitution of the oxygens in NQ for the CH2 groups in NQDM increases, rather than decreases, the singlet-triplet energy separation (EST).

Cite

Export

Save

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1508275

Report Number(s):: PNNL-SA-131464

Journal Information:: Journal of Physical Organic Chemistry, Vol. 31, Issue 8; ISSN 0894-3230

Country of Publication:: United States

Language:: English

References (23)

Potential surface for the methylenecyclopropane rearrangement Feller, David; Tanaka, Kiyoshi; Davidson, Ernest R. Journal of the American Chemical Society, Vol. 104, Issue 4 https://doi.org/10.1021/ja00368a007	journal	February 1982
Electronic Structure and Spectroscopy of Oxyallyl: A Theoretical Study Mozhayskiy, Vadim; Goebbert, Daniel J.; Velarde, Luis The Journal of Physical Chemistry A, Vol. 114, Issue 26 https://doi.org/10.1021/jp102183z	journal	July 2010
On the Electronic Structures and Electron Affinities of the m -Benzoquinone (BQ) Diradical and the o -, p -BQ Molecules: A Synergetic Photoelectron Spectroscopic and Theoretical Study Fu, Qiang; Yang, Jinlong; Wang, Xue-Bin The Journal of Physical Chemistry A, Vol. 115, Issue 15 https://doi.org/10.1021/jp1120542	journal	April 2011
Second‐order perturbation theory with a complete active space self‐consistent field reference function Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O. The Journal of Chemical Physics, Vol. 96, Issue 2 https://doi.org/10.1063/1.462209	journal	January 1992
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Diradicals Abe, Manabu Chemical Reviews, Vol. 113, Issue 9 https://doi.org/10.1021/cr400056a	journal	July 2013
Photoelectron spectroscopy of the trimethylenemethane negative ion Wenthold, Paul G.; Hu, Jun; Squires, Robert R. Journal of the American Society for Mass Spectrometry, Vol. 10, Issue 9 https://doi.org/10.1016/S1044-0305(99)00043-4	journal	September 1999
Ab initio calculations on m-quinone. The ground state is a triplet Fort, Raymond C.; Getty, Stephen J.; Hrovat, David A. Journal of the American Chemical Society, Vol. 114, Issue 19 https://doi.org/10.1021/ja00045a031	journal	September 1992
Photoelectron Spectroscopic Study of the Oxyallyl Diradical Ichino, Takatoshi; Villano, Stephanie M.; Gianola, Adam J. The Journal of Physical Chemistry A, Vol. 115, Issue 9 https://doi.org/10.1021/jp111311k	journal	March 2011
Spin-conserving and spin-flipping equation-of-motion coupled-cluster method with triple excitations Slipchenko, Lyudmila V.; Krylov, Anna I. The Journal of Chemical Physics, Vol. 123, Issue 8 https://doi.org/10.1063/1.2006091	journal	August 2005
The Negative Ion Photoelectron Spectrum of meta -Benzoquinone Radical Anion (MBQ ^•– ): A Joint Experimental and Computational Study Chen, Bo; Hrovat, David A.; Deng, S. H. M. Journal of the American Chemical Society, Vol. 136, Issue 9 https://doi.org/10.1021/ja412433t	journal	February 2014
The Electronic Properties of Diradicals Salem, Lionel; Rowland, Colin Angewandte Chemie International Edition in English, Vol. 11, Issue 2 https://doi.org/10.1002/anie.197200921	journal	February 1972
Structure and stability of oxyallyl. An MCSCF study Osamura, Yoshihiro; Borden, Weston T.; Morokuma, Keiji Journal of the American Chemical Society, Vol. 106, Issue 18 https://doi.org/10.1021/ja00330a013	journal	September 1984
The Lowest Singlet and Triplet States of the Oxyallyl Diradical Ichino, Takatoshi; Villano, Stephanie M.; Gianola, Adam J. Angewandte Chemie International Edition, Vol. 48, Issue 45 https://doi.org/10.1002/anie.200904417	journal	October 2009
Ab initio MCSCF and CI calculations of the singlet-triplet energy differences in oxyallyl and in dimethyloxyallyl Coolidge, Michael B.; Yamashita, Koichi; Morokuma, Keiji Journal of the American Chemical Society, Vol. 112, Issue 5 https://doi.org/10.1021/ja00161a015	journal	February 1990
Trimethylenemethane. Comparison of Multiconfiguration Self-Consistent Field and Density Functional Methods for a Non-Kekulé Hydrocarbon Cramer, Christopher J.; Smith, Bradley A. The Journal of Physical Chemistry, Vol. 100, Issue 23 https://doi.org/10.1021/jp953697x	journal	January 1996
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K. Journal of Computational Chemistry, Vol. 37, Issue 5 https://doi.org/10.1002/jcc.24221	journal	November 2015
Photoelectron Spectroscopy of the Trimethylene- methane Negative Ion. The Singlet−Triplet Splitting of Trimethylenemethane ^† Wenthold, Paul G.; Hu, Jun; Squires, Robert R. Journal of the American Chemical Society, Vol. 118, Issue 2 https://doi.org/10.1021/ja9532547	journal	January 1996
The synergy between qualitative theory, quantitative calculations, and direct experiments in understanding, calculating, and measuring the energy differences between the lowest singlet and triplet states of organic diradicals Carl Lineberger, W.; Thatcher Borden, Weston Physical Chemistry Chemical Physics, Vol. 13, Issue 25 https://doi.org/10.1039/c0cp02786c	journal	January 2011
An exceptionally simple method of preparation of biradicals. 2. Low-temperature fluorescence spectra and ambient temperature laser-induced fluorescence spectra of 1,3-, 1,6-, 2,6-, and 2,7-naphthoquinodimethane Biewer, Michael C.; Biehn, Curtiss R.; Platz, Matthew S. Journal of the American Chemical Society, Vol. 113, Issue 2 https://doi.org/10.1021/ja00002a033	journal	January 1991
Photoelectron Spectroscopy of m -Xylylene Anion Wenthold, Paul G.; Kim, Joseph B.; Lineberger, W. C. Journal of the American Chemical Society, Vol. 119, Issue 6 https://doi.org/10.1021/ja9623830	journal	February 1997
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
The Importance of Including Dynamic Electron Correlation in ab Initio Calculations Borden, Weston Thatcher; Davidson, Ernest R. Accounts of Chemical Research, Vol. 29, Issue 2 https://doi.org/10.1021/ar950134v	journal	January 1996

Similar Records

Negative Ion Photoelectron Spectroscopy Confirms the Prediction of the Relative Energies of the Low-Lying Electronic States of 2,7-Naphthoquinone

Journal Article · Thu May 31 00:00:00 EDT 2018 · Journal of Physical Chemistry A · OSTI ID:1508275

Yang, Zheng; Hrovat, David; Hou, Gao-Lei; +2 more

Calculations on 1,8-naphthoquinone predict that the ground state of this diradical is a singlet: Calculations on 1,8-Naphthoquinone Predict that the Ground State of this Diradical Is a Singlet

Journal Article · Wed Oct 03 00:00:00 EDT 2018 · Journal of Computational Chemistry · OSTI ID:1508275

Hrovat, David A.; Wang, Xue-Bin; Borden, Weston Thatcher

Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical

Journal Article · Thu Mar 14 00:00:00 EDT 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1508275

Yang, Zheng; Hrovat, David A.; Hou, Gao -Lei; +2 more

Title: Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST )

Citation Formats

References (23)

Similar Records

Related Subjects

Title: Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH ₂ is predicted to increase the singlet-triplet energy difference ( ΔE _ST )